US3294875A - Phosphoric acid esters, ester amides or ester diamides - Google Patents
Phosphoric acid esters, ester amides or ester diamides Download PDFInfo
- Publication number
- US3294875A US3294875A US264716A US26471663A US3294875A US 3294875 A US3294875 A US 3294875A US 264716 A US264716 A US 264716A US 26471663 A US26471663 A US 26471663A US 3294875 A US3294875 A US 3294875A
- Authority
- US
- United States
- Prior art keywords
- ester
- compound
- phosphoric acid
- methyl
- acid esters
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 ester amides Chemical class 0.000 title description 16
- 150000003014 phosphoric acid esters Chemical class 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 34
- 239000000243 solution Substances 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 125000003282 alkyl amino group Chemical group 0.000 description 11
- 125000004663 dialkyl amino group Chemical group 0.000 description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 9
- 241000255925 Diptera Species 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 241001124076 Aphididae Species 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 241001454295 Tetranychidae Species 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 241000607479 Yersinia pestis Species 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 241000238631 Hexapoda Species 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 241001425390 Aphis fabae Species 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000255581 Drosophila <fruit fly, genus> Species 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 241000700159 Rattus Species 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003151 ovacidal effect Effects 0.000 description 2
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009885 systemic effect Effects 0.000 description 2
- 241000238876 Acari Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000122098 Ephestia kuehniella Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241000256602 Isoptera Species 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 241001325166 Phacelia congesta Species 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241001454293 Tetranychus urticae Species 0.000 description 1
- 240000006677 Vicia faba Species 0.000 description 1
- 235000010749 Vicia faba Nutrition 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 244000078703 ectoparasite Species 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 231100000194 ovacidal Toxicity 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/242—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyaryl compounds
Definitions
- the present invention relates to and has as its objects new and useful insecticidally active phosphorous containing compounds. More specifically this invention is concerned with phosphoric acid esters, ester amides or ester diamides of the general formula In the aforesaid formula R and R stand for lower alkyl radicals preferably with l to 4 carbon atoms and X and Y for the same or different alkoxy, amino, alkylamino, or dialkyla-mino groups, while n is a whole number from 2 to 4.
- the said O-phenyl-phosphoric acid dichlorides are reacted, optionally in the presence of acid-binding agents, with preferably lower alcohols, ammonia or alkylor dialkylamines. In the reaction with amines an excess of the latter can serve as acid-binding agent.
- the reaction according to the process is in general performed in an inert organic solvent.
- Lower aliphatic ketones e.g. acetone, methyl ethyl ketone
- optionally chlorinated aliphatic or aromatic hydrocarbons have proved most valuable for this purpose.
- the reaction temperature is variable within wide limits, but lies expediently between and 100 C.
- alkyl-substituted O-(alkyl-mercaptophenyl)-phosphoric acid dichlorides needed as starting materials for the last mentioned variant of the process can be obtained according to known methods by reaction of the corresponding alkyl-alkyl-mercaptophenols with phosphorous oxychloride.
- inventive products are in part viscous, substantially water-insoluble colorless to brown-yellow coloured oils, but partly occur also in the form of crystalline substances of sharp melting point which can easily be further purified by recrystallisation from the usual solvents.
- the compounds according to the invention are distinguished by outstanding pesticidal properties and therefore they are valuable pest combating agents with a wide range of activity which besides an excellent insecticidal and acaricidal activity, also show an ovicidal, nematodicidal and termite-combating effect.
- the new compounds of the present invention very effectively kill insects like aphids, spider mites, caterpillars, flies etc. They distinguish themselves especially by a good contact-insecticidal activity and mostly also by a systemic action. At the same time they have an activity on eating insects such as caterpillars. Most surprisingly they are of remarkable low toxicity against mammals. They may be used in the same manner as other known phosphoric insecticides, i.e. in a concentration from about 0,0000l% to about 1%, diluted or extended with suitable/solid or liquid carriers or diluents.
- alcohols especially lower alcohols such as methanol or ethanol
- ketones especially lower ketones such as acetone or methyl ethyl ketone
- water if necessary with commercial emulsifiers
- alcohols especially lower alcohols such as methanol or ethanol
- ketones especially lower ketones such as acetone or methyl ethyl ketone
- liquid hydrocarbons and the like examples of such solid carriers there may be mentioned water (if necessary with commercial emulsifiers), alcohols, especially
- inventive compounds of the following formulae have been tested against aphids, spider mites (compounds I, II and III) and flies (compound I).
- Aqueous dilutions of these compounds have been prepared by mixing the active ingredients with the same amounts of dimethyl formamide as an auxiliary solvent adding thereto 20% by weight referred to active ingredient of a commercial emulsifier consisting of a benzyl hydroxy polyglycol ether containing about 10 to 15 glycol ethers, and diluting this premixture at last with water to the desired concentration indicated in the following paragraphs:
- flies about 50 flies (Drosophila) are placed under covered petri dishes in which drip wet filter papers have been placed which are sprayed with insecticidal solutions of concentrations as shown below. The living status of the flies has been determined after 24 hours. The following results have been obtained:
- Aqueous concentration in Killing rate Compound percent active ingredient/ (in percent) water
- Example 1 HaG-S O-P OCtHs H3O 50.5 g. of 3,5-dirnethyl-4-methylmercaptophenol are dissolved in 250 ml. of benzene. This solution is mixed with 135 ml. of a 2.23 normal methanolic sodium methylate solution and the methanol and benzene is then distilled oflfinally in a vacuum at a bath temperature of 160 C. maximum. The remaining sodium salt of the abovementioned phenol is dissolved at 50 C. in 210 ml. of anhydrous methyl ethyl ketone, and to this solution 5 3 g. of 0,0-diethyl phosphoric acid chloride are added dropwise at 50 C. with external cooling.
- reaction mixture is then boiled for a further hour .under reflux and the solvent is removed by distillation in a vacuum.
- the remaining residue is taken up in400 ml. of benzene, the benzenic solution is washed with water, 1 N sodium hydroxide solution, and again with water and dried over sodium sulphate.
- the 0,0-diethyl-O-(3,5-dimethyl 4-methylmercaptophenyl)- phosphoric acid ester is obtained by distillation of the residue in a high vacuum, where it distils under a pres- :sure of 0.001 mm. Hg at 135 C.
- the yield amounts to 458.5 g.
- Spider mites are killed to by 0.01% solutions of the compound, termites to by 0.05% solutions. When administered in a concentration of 0.1% the preparation is 100% systemically effective.
- Concentration of active agent in percent Killing rate of pests, in percent Administration against 1 Ovicidal activity.
- Example 5 6H NHCHa Gaseous methylamine is conducted into a solution of 28.5 g. (0.1 mol) of 3,5-dimethyl-4-methyl-mercaptophenyl-phosphoric acid dichloride (MP. 72 to 73 C.) in benzene at O to 10 C. with stirring and external cooling of the mixture with ice. After the reaction is completed, the reaction mixture is further stirred for 3 hours at room temperature, the precipitated methyl ammonium hydrochloride is dissolved by the addition of water and the organic phase Washed with water until it gives a neutral reaction. The mixture is then worked up in the same manner as described in the preceding examples. There remain 18.5 g. (67.5 g.
- R and R' stand for lower alkyl having up to 4 carbon atoms
- X stands for a member selected from the group consisting of lower alkoxy, lower alkyl amino and lower dialkyl amino, alkyl and alkoxy in each case having up to 4 carbon atoms
- Y stands for a member selected from the group consisting of lower alkyl amino and lower dialkyl amino, alkyl in each. case having up to 4 carbon atoms and It stands for 2.
- a compound of the formula 0 X cfi. s@-o l wherein X stands for a member selected from the group consisting of lower alkoxy, lower alkyl amino and lower dialkyl amino, alkyl and alkoxy in each case having up to 4 carbon atoms and Y stands for lower alkyl amino and lower dialkyl amino, alkyl in each case having up to 4 carbon atoms.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Fertilizers (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF36280A DE1160436B (de) | 1962-03-15 | 1962-03-15 | Verfahren zur Herstellung von Phosphorsaeureestern, -esteramiden bzw. -esterdiamiden |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3294875A true US3294875A (en) | 1966-12-27 |
Family
ID=7096375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US264716A Expired - Lifetime US3294875A (en) | 1962-03-15 | 1963-03-12 | Phosphoric acid esters, ester amides or ester diamides |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3294875A (pt) |
| BE (1) | BE629625A (pt) |
| CH (1) | CH430319A (pt) |
| DE (1) | DE1160436B (pt) |
| DK (1) | DK107396C (pt) |
| GB (1) | GB975354A (pt) |
| NL (2) | NL137339C (pt) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2978479A (en) * | 1958-03-08 | 1961-04-04 | Bayer Ag | Pest control agents |
| US3042703A (en) * | 1956-03-22 | 1962-07-03 | Bayer Ag | Thiophosphoric acid esters and their production |
| US3056825A (en) * | 1958-02-12 | 1962-10-02 | Bayer Ag | Thiophosphoric acid esters and a process for their production |
| US3092544A (en) * | 1961-11-03 | 1963-06-04 | Dow Chemical Co | Organo phosphorous nematocide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL214246A (pt) * | 1956-04-02 | |||
| AT213903B (de) * | 1958-03-08 | 1961-03-10 | Bayer Ag | Verfahren zur Herstellung neuer Alkylmercapto-phenyl-phosphorsäure- bzw.-thionophosphorsäure-esteramide bzw.-diamide |
| LU37845A1 (pt) * | 1958-07-22 |
-
0
- NL NL289967D patent/NL289967A/xx unknown
- NL NL137339D patent/NL137339C/xx active
- BE BE629625D patent/BE629625A/xx unknown
-
1962
- 1962-03-15 DE DEF36280A patent/DE1160436B/de active Pending
-
1963
- 1963-03-01 CH CH262863A patent/CH430319A/de unknown
- 1963-03-12 US US264716A patent/US3294875A/en not_active Expired - Lifetime
- 1963-03-13 DK DK115963AA patent/DK107396C/da active
- 1963-03-14 GB GB10146/63A patent/GB975354A/en not_active Expired
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3042703A (en) * | 1956-03-22 | 1962-07-03 | Bayer Ag | Thiophosphoric acid esters and their production |
| US3056825A (en) * | 1958-02-12 | 1962-10-02 | Bayer Ag | Thiophosphoric acid esters and a process for their production |
| US2978479A (en) * | 1958-03-08 | 1961-04-04 | Bayer Ag | Pest control agents |
| US3092544A (en) * | 1961-11-03 | 1963-06-04 | Dow Chemical Co | Organo phosphorous nematocide |
Also Published As
| Publication number | Publication date |
|---|---|
| CH430319A (de) | 1967-02-15 |
| NL289967A (pt) | |
| DK107396C (da) | 1967-05-22 |
| DE1160436B (de) | 1964-01-02 |
| GB975354A (en) | 1964-11-18 |
| BE629625A (pt) | |
| NL137339C (pt) |
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